Delustering



Patented Apr. 25,v 1933 UNITED gsTATas HENRY A. GARDNER, oF WASHINGTON, DISTRICT or commen;

DEnUsmIN'G dillo Ilhawing..z l yapplicationA led Julyfzl, This invention relates to delustering; and

it comprises afprocess ofproducing opalescence, or a flat finlsh, as the case may bfe,'1n

fibers, films, varnishes, lacquers', etc.,fwhere 5 in an organosol of a metalllcoxid, advanta- 20 moredesirable. Opacity and, to some extent,

latnes's can be and are attainedby the useof the ordinary line fillers mixed Awith the c'omposition, such as barium sulfate or titanium dioxid ;-but these materials as commercially 25 obtainable are too coarse' grained to get'the best lresultsirom'an'optical point of view.

` It is the object of the present invention to provide anew ,method of obtaining opalescence or ilatness, as the case may be, giving 0 superior results.l To this end, I utilize the opticalv properties of organosols of metallic oxids; producing an extremelyjine dispersion of various metallic oxids in solvents employed for making films and filaments by adding to the solvent,"an'alkylated compound of the metal and permitting hydrolysis therein. The alkylated materials best ladapted for lmy purposes in giving vtranslucen'ce are those derived from TiO2` and ZrOz, al`k lg1 4 though 'i multiplicity of other metallic Oxids can be used, some ofthese being hereinafter indicated. While it isordinarily assumed that neither titanium or zirconium gives alkylate derivatives, Il have found that these can be easily made by processes described post. These alkylate derivatives dissolved in organic liquids are sensitive to moisture and can be readily hydrolyzed to give'organolsols.

The alkylated compounds of metals'which areuseful the present 'of the alcoholate type. They may be representedby f v 55 wherein` Ml represents f a ymetal and f R frepresentsanv alkyl group. Of course-thefnumber `oi. alcoholic'lresidues required to ysatisfy the valenceof the metal are present. When hydrolyzed, these alcoh'ol'ated compounds of'BO 'n Y metal, or. metal alcohola'ites',"'yield metallic oxids or hydrated oxids which generally are insoluble l in organic solvents, particularly vthose organic solvents commonly? used with cellulose esters` and ethers in' compounding 65 compositions for' theI manufacture of farti- 'ficlalzfsilks and the'vlike. In formingthe organosols'required in the'present invention Itis essential that them'etallic 'oxid or hydrated'oxid'jprodu'cedbyhydrolysis be s'ub-y vI0 i stantially .insoluble i in 'the particular organic liquid used. Y n ff L Speaking more specifically off ,titanium compounds, vtitanium tetrachlorid can be 'convertedinto titanium tetraeth'ylate by the valc-"'15 tion of metallicv sodium and ethyl alcohol, sodium ethylate beingpr'obably first formed. The sodium chlorid produced is insol1"1bleand can be readily separated from the liquidproducts of reaction. The new compound pro- 80 duced, titaniumf-vtetraethylate, 1 whenkr freed from vany excess lof alcohol`,-is" a" thin, mobiler' liquid withl a' boilingpoint of200y Gl'at'156 mm. Y It 4can -be vacuum" ydistilled Vto recover 1t; or 1t can be left in the alcoholic so- 35 lution `in `which itis made. Itis solu- Vble in the usualorganic' solvents, but is'rea'dily decomposedby evenftraces of moisture; ving an veidiremely line'dispersion or organosol of TiO2 ;v probably in hydrated "form,v i ora's the so-'called titanic acid. Zirconium tetraethylate may be made by -a similar method and has similar'properties. Zirconium tetraethylate mayalso be distilled'under vacuum. Lower-boiling but similar com- 195 pounds may be madeby using methyl alcohol in lieu of ethyl alcohol; and still'higher boiling compounds by the `use ofthe hi lier :ilcohols, propl; butyl, pentyl, etcl y yese ual-k kylated titanium and zirconium compounds 100 v f of water, hydrolysis at once occurs.

stfl'jellyl isl'formedby the waterpresent are soluble in a variety of organic liquids, including alcohol, light petroleum distillates and toluol.

Solutions of any of these alkylated compounds in absolute alcohol, hydrocarbons, etc., are clear, but on addition of even tralies C.. cording to the quantity `of' alkylated derivatives present, the resultmay vary from a simple opalescence to the formation of a st gel or jelly. Because of the extremely neipar-g ticle size in these dispersions, all the sols and gels produced are `translucent rather than opaque. For example, by adding l cc.V of titanium tetraethylate to 10 cc. oa mixture of 95 1percent alcohol and ether, a dense,

in the alcohol'. Thejelly is howevenquite translucent, indicating an extreme `lineness of subdivision in the TiOZ formed.

y y The (present invention maybeutilized in many rections. 1 Inmaking varnishes and lacquers opalescent to` transmitted light and Hat to reflected light, a small amount of titanium tetraethylate or one oftheother alkylated compounds mentioned may be added to one of the solvents used in making the varnish `or lacquer. In making automobile lacquers, for example, opalescent or fiat, an ordinary lacquer is mixed with alittle titanium tetraethylate, dissolvedin alcohol or toluol. t Ordinarily,ithere `is enough moisture present in the lacquer to produce the desired organosol. The present invention is even of advantage where the lacquer carries `incorporated pigment in amount sulicient tomake it opaque, since it destroys the luster of the surface layersofthe drylacquer and gives a flat effect. Similarly,` titanium tetraethylate, or oneof the other compounds mentioned, may be dissolved in an anhydrous solvent and added to the compositionsused in making.

Celluloid articles,` nitrocellulose threads (tChardonnet silk), acetyleellulose threads, e c. i i y Iregard thepresent invention as particularly useful with articial silk made from either vnitrocellulose or acetylcellulose,fsince it lenables theproduction-of a silky opalescence, obviatng the high luster of the ordinary threads. Arn additional advantageyis the greater ease of dyeing of the delustered threads, since titanium hydroxid and zirconium hydroxid are excellent mordants; their presence enabling the use of a wide variety of dyes not otherwise applicable to these artiicial Silks. l ,y

`The color, of the `dispersed vparticles of TiOz` or ZrO2 is White and they give a pearly orsilky opalescence; but the particles may be dyed any color, giving a correspondingly tinted opalescence. This may be done by dissolving a basic dye in the alkylatesolution. On hydrolysis, the hydroxid particles take up or adsorb the dye. y t

In a specific embodiment of the present invention, employing titanium tetraethylate to make delustered silk with a silky opalescence, l part by volume of liquid titanium tetraethylate was dissolved in 10 parts of absolute alcohol. parts of a mixture of ethyl ether and alcohol in the lproportion of 60:40, the alcohol being ordinary V95 per cent.` A white but translucent jelly formed. `Nitrocellulose in the proportion of 25 per cent by weight was added and the mixture stirred until a good solution was obtained. The translucent preparation `obtained was forced through capillaries to form threads in the usual meth- `od adoptedtoform` artificial silk; the liber `being subsequently denitrated and y otherwise processed as usual.`` The iinal delusteredsilk had `a translucent, dull appearance like that of natural silk. ,While I added thetitanium tetraethylate to thealcohol-ether before dissolving the nitrocellulose, the nitrocellulose "Cellulose acetate silk and nitrocellulose "silk, formed vinthe manner just described both have the silky translucency of natural silk and `thegeneral appearance of natural fsilk; Unique silks maybe made by adding a' small proportion of .a basic dye to the solution of titanium orzivrconium tetraethylate. On hydrolysis, the very finely dispersedparticles of hydroxid are tinted and the resulting silk has a peculiar tinted opalescence.

By the useofa verysmall amount of ablue dye, a brilliant white opalescence is obtained, this `amount of `blue dye serving to compensatefor the natural yellovvof the ber.

While I` have` spoken" more specifically "of A titanium` and "mzirconium compounds and while I regard 'them` best adapted for my purposes, a Wide variety of other metals forming alkyl derivaties hydrolyzed by Water may bepused in their lieu. `Aluminum, magnesium and zincvcompounds may be mentioned. `f `For special purposes,V metals having colored oxids,` such` as cobalt and nickel, maybe used.,` While "cobalt and nickel are not presumed to form directy connected alkyl derivatives, their chlorids, bromids and iodids in alcoholic solution will give dialkylated derivatives on treatment with sodium.

Linseed oil treated according to the present invention, by` convertingit into an or The solution was mixed with 1004 ganosol of cobalt, manganese, vanadium orv lead oxid, is not only converted into a form drying with a fiat lfinish but also one which dries quickly; the finely dispersed particles of the hydrated oxids of these metals produced in the present manner being unusually y active Aas catalysts in promoting drying.

What I claim is 1. In the production of artificial silk having an opalescent silkyA translucence from an artificial silk composition, comprising a cellulose material of the class consisting of cellulose esters and ethers, andan organic liquid component, the steps which comprise adding al hydrolyzable alkylated compound of metal to an organic liquid component of said artificial silk composition in the presence of moisture and thereafter forming filaments of artificial silk from said artificial silk composition containing said liquid organic component. c y

2. In the production of artificial silk having anvopalescent silky translucence by the process of claim 1 in which a hydrolyzable alkylated compound of zirconium is used.

' '3. In the production of artificial silk having an opalescent silky translucence by extrusion of a cellulosic solution, the process which comprises developing by hydrolysis of an alkylated compound of a metal, a

metallic oxid dispersion, in situ, within said cellulosic solution prior to the extrusion thereof.

. 4. In the production of artificial silk having an opalescent silky translucence by extrusion of a cellulosic solution, the process which comprises developing a metallic oxid y dispersion within said cellulosic solution,

-`dyein the said metallic oxid dispersion and extru ing the resulting product.

5. In the manufacture of delustered materials from cellulose materials of the class` consisting of cellulose esters and ethers, the process which comprises admixing a liquid alkylate of a metal with a liquid capable of dissolving said material and containing sufficient water to hydrolyze said metallic alkylate, dissolving said material in the mixture thus obtained and extruding said mixture.

6. In the manufacture of delustered materials from nitrocellulose, the process which comprises mixing a liquid ethylate of a metall i vent, adding a vobtainedy mixturer of ethyl ether and alcohol containing suicientfvvater to hydrolyze said u ezthylate, lthuis hydrolyzing "saidl,ethylate' and producing a` f :olloidal'V v,disper-v.

sion, `dissolving nitrocellulose in` thejmixture 70.

thus obtained and extrudingsaid mixture.

10..-Inpthelmanufacture of delustered materials" from cellulose acetate, the process which 'comprises dissolving cellulose acetate in acetone, addingV to the solution thus .0b-`r tained a solution of an alkylate of a metal ture thus obtained.

11. The process of claim 10 in which they said alkylate isA zirconium' tetraethylate.

-dissolved in absolute alcohol, hydrolyzing the l said alkylate in situ, and extruding themix-` 12. In the manufacture of delustered materials from cellulose acetate, the process'- which comprises dissolving cellulose acetate in a suitable solvent, adding to the solution,

thus obtained a solution of an alkylate of a metal, hydrolyzing saidalkylate in solution i and extruding the mixture thus obtained.

13. In the manufacture of delustered materials from cellulose ethers and esters, the process wlnch comprises dissolving such substances 1n a suitable solvent, saldsolvent containing suliicient Water to hydrolyze an alky- Y late of a metal, addin to the solution thus, f

obtained an alkylate o a metal, hydrolyzing' the said alkylate in situy andextruding the mixture thus obtained.

14. In the manufacture of delustered, colored materials from cellulose esters andethers, the process which comprises'dissolving such substances in a suitable solvent, admixing the solution thus vobtained With a solution comprising an alkylate of a metal, a dye and a solvent in which the said alkylate is soluble, hydrolyzing the alkylate and dyeing the colloidal particles of the -metallic hydroxide and oxide thus produced with the said dye and extruding the colored mixture thus obtained to produce said delustered colored materials.

15. In the manufacture of delustered, colored materials from cellulose esters and ethers, the process which comprises dissolving an alkylate of a metal in a suitable soldye to thel solution thus ob-, tained, hydrolyzing the alkylate in situ thus producing a colloidal dispersion of metallic -hydroxid or oxid and dyeing the colloidal particles thus produced, mixing the colloidal dispersion thus obtained with a cellulose mixture thus obtained to produce said delustered colored materials.

16. The production of delustered artificial silk bythe method of claim l, wherein saidV is added to the said organic liquid component prior to mixing with the said cellulose 'material.

17. The production of delustered artificial `ester or etherand extruding the colored im hydrolyzable alkylated compound of metal 

